EP0102112B1 - Verfahren zur Wasserstoffbehandlung von Schweröl - Google Patents

Verfahren zur Wasserstoffbehandlung von Schweröl Download PDF

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Publication number
EP0102112B1
EP0102112B1 EP19830201140 EP83201140A EP0102112B1 EP 0102112 B1 EP0102112 B1 EP 0102112B1 EP 19830201140 EP19830201140 EP 19830201140 EP 83201140 A EP83201140 A EP 83201140A EP 0102112 B1 EP0102112 B1 EP 0102112B1
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EP
European Patent Office
Prior art keywords
reactor
hydrocarbon mixture
process according
heavy oil
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19830201140
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English (en)
French (fr)
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EP0102112A3 (en
EP0102112A2 (de
Inventor
Leonardus Johanna Van Aubel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of EP0102112A2 publication Critical patent/EP0102112A2/de
Publication of EP0102112A3 publication Critical patent/EP0102112A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00

Definitions

  • the invention relates to a process for the hydrotreating of a heavy oil by leading the heavy oil and hydrogen at elevated temperature and pressure cocurrently in downward direction through a reactor which contains at least one bed of a solid catalyst.
  • hydrotreatment is used for conversion processes in which heavy oils are converted in the presence of hydrogen. These conversion processes comprise in particular demetallization, desulphurization, denitrogenation, asphaltene conversion and hydrocracking.
  • heavy oils is used in this specification and claims for mixtures of hydrocarbons which are at least for the greater part in the liquid phase at the conditions of temperature and pressure prevailing in the reactor during normal operation of the hydrotreating process.
  • heavy oils may be mentioned crude mineral oils, topped mineral oils, residues of atmospheric or vacuum distillation of mineral oils, deasphalted residual oils, asphalts, shale oils, oils obtained from tar sands.
  • Hydrotreatment of heavy oils is conventionally carried out by passing the oil together with hydrogen (in this specification the word hydrogen stands for pure hydrogen as well as for hydrogen-containing gases) in downward direction through a reactor which contains at least one bed of a solid catalyst.
  • the heavy oil also called the feed
  • This cooling capacity also called heat-sink
  • the hydrogen containing gas which may include recycle gas
  • the present invention relates to a process for the hydrotreating of a heavy oil by leading the heavy oil and hydrogen at elevated temperature and pressure cocurrently in downward direction through a reactor which contains at least one bed of a solid catalyst, in which process also a hydrocarbon mixture, which is at least for the greater part in the gaseous phase at the conditions prevailing in the reactor, is introduced into the reactor at a point upstream of the uppermost bed of solid catalyst.
  • the hydrocarbon mixture which is at least for the greater part in the gaseous phase at the conditions prevailing in the reactor is very suitably brought at reactor pressure in the liquid state with the aid of a pump. In this way the need for using gas compressors with a high capacity is overcome. Part of this hydrocarbon mixture may evaporate between the said pump and its entrance into the reactor owing to heating or heat exchange with other streams.
  • the said hydrocarbon mixture will act as a heat sink in the first reactor bed due to its heat capacity and heat of evaporation, and it may replace part of the hydrogen-containing gas in this respect during normal operation. It is preferred that such an amount of said hydrocarbon mixture is introduced into the reactor that temperature runaway in the uppermost catalyst bed does not occur when the supply of heavy oil or hydrogen is interrupted.
  • the hydrocarbon mixture which is at least for the greater part in the gaseous phase at the conditions prevailing in the reactor and which is introduced into the reactor at a point upstream of the uppermost bed of solid catalyst very conveniently consists of a fraction of the reactor effluent.
  • the effluent of the reactor which consists of hydrotreated heavy oil and a hydrogen-containing gas is separated in high temperature (“hot”) separators and low temperature (“cold”) separators consecutively, yielding gaseous and liquid products.
  • Hot high temperature
  • cold low temperature
  • Liquid product from the cold separators (which consists of condensable compounds of the gaseous product from the hot separators) is very suitable to be used as the said hydrocarbon mixture.
  • the amount of said hydrocarbon mixture, preferably liquid product from the cold separators, which is to be introduced in order to have available sufficient cooling capacity to avoid temperature runaway in the uppermost catalyst bed under all circumstances, even in case the feed supply or the hydrogen supply is interrupted, will depend on the type of feed, the type and degree of feed conversion to be achieved during normal operation, the reaction conditions and the catalyst. For each specific case the minimum amount of the said hydrocarbon mixture which is to be introduced into the reactor must be determined by experiments on a small scale and/or calculations.
  • the composition of the catalyst will be adapted to the reaction desired.
  • the supports very conveniently being amorphous refractory oxides (or mixtures thereof) of elements of Group II, III and IV of the Periodic Table of Elements e.g. magnesia, silica, alumina, zirconia, silica-alumina, silica-zirconia.
  • Supports consisting of crystalline materials, such as zeolites may also be used.
  • One or more metals (and/or compounds thereof) with hydrogenating activity are very suitably present onto the supports, in particular metals of Group VB, VIB, VIIB and/or VIII of the Periodic Table of Elements.
  • metals of Group VB, VIB, VIIB and/or VIII of the Periodic Table of Elements For example, in case hydrodesulphurization is the most desired reaction to take place, catalysts which contain compounds of cobalt and/or nickel together with compounds of molybdenum and/or tungsten on alumina as a support are very suitable.
  • hydrodemetallization is the most desired reaction, catalyts based on silica as a support and containing only compounds of molybdenum, or a combination of compounds of nickel and vanadium, respectively, are very convenient.
  • the catalyst particles present in the beds may have any suitable form, e.g. powders, spheres, pellets, cylindrical extrudates, multilobed extrudates, rings and the like. Cylindrical extrudates with a diameter from 0.5 to 2.5 mm are very suitable in general.
  • reaction conditions prevailing in the reactor will be adapted to the hydrotreating reaction desired. In general, temperatures from 300-450°C, total pressures from 25-300 bar, hydrogen partial pressures from 25-250 bar, and space velocities of 0.1-10 kg feed per kg catalyst per hour will be very suitable.
  • the catalyst in the form of extrudates with 0.8 mm diameter
  • the catalyst consists of an alumina support onto which nickel oxide and molybdenum oxide have been applied; the catalyst is sulphided before use.
  • the feed of fresh hydrogen containing gas (95% vol. pure hydrogen, 5% vol. methane) is 225 nm 3 /ton feed.
  • the off-gas of the reactors is (after removal of H 2 S) recycled and introduced into the reactor upstream of the first catalyst bed. The gases are led over the catalyst concurrently with the feed.
  • the reactor pressures are adapted so as to have an average hydrogen partial pessure of 150 bar in all cases.
  • the average reactor temperature is 380°C.
  • the amount of recycle gas in experiment 1 as well as the amount of recycle gas together with the amount of hydrocarbon mixture in experiment 2 are sufficient to avoid temperature runaway in case the feed flow is interrupted. From the table it can be seen that the pressure drop (Ap) in experiment 1 (73 bar) is much higher than that in experiment 2 (14 bar). In order to overcome the pressure drop the pressure at the inlet of the first reactor must be higher in experiment 1 than in experiment 2. Accordingly the equipment of experiment 1 must be designed to withstand higher pressures than that of experiment 2, which of course is unattractive from an economical point of view. Moreover, the gas compressor for the recycle gas can be much smaller in experiment 2 than in experiment 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (9)

1. Ein Verfahren zur Hydrobehandlung eines Schweröls, indem man das Schweröl und den Wasserstoff bei erhöhter Temperatur und erhöhtem Druck im Gleichstrom abwärts durch einen Reaktor leitet, welcher mindestens ein Bett eines festen Katalysators enthält, in welchem Verfahren auch eine Kohlenwasserstoffmischung, welche zumindest zum größeren Teil unter den im Reaktor herrschenden Bedingungen in der gasförmigen Phase vorliegt, in den Reaktor an einem stromaufwärts bezüglich des obersten Bettes des festen Katalysators gelegenen Punkt eingeführt wird.
2. Ein Verfahren nach Anspruch 1, in welchem die Kohlenwasserstoffmischung im flüssigen Zustand mit Hilfe einer Pumpe auf Reaktordruck gebracht wird.
3. Ein Verfahren nach Anspruch 1 oder 2, in welchem die Kohlenwasserstoffmischung kontinuierlich eingeführt wird.
4. Ein Verfahren nach einem der vorstehenden Ansprüche, in welchem die Kohlenwasserstoffmischung eine Fraktion des Reaktoraustragsstroms ist.
5. Ein Verfahren nach einem der vorstehenden Ansprüche, in welchem die Kohlenwasserstoffmischung als flüssiges Produkt aus einer Niedrigtemperatur-Trennvorrichtung für den Reaktoraustragsstrom erhalten wird.
6. Ein Verfahren nach einem der vorstehenden Ansprüche, in welchem die Kohlenwasserstoffmischung in den Reaktor eingespeist wird mittels einer Vorrichtung, welche unabhängig ist von der Einspeisvorrichtung für das der Hydrobehandlung zu unterwerfende Schweröl.
7. Ein Verfahren nach einem der vorstehenden Ansprüche, in welchem die Menge der in den Reaktor eingespeisten Kohlenwasserstoffmischung so groß ist, daß kein Durchgehen der Temperatur im obersten Katalysatorbett stattfindet, wenn die Schwerölzufuhr oder die Wasserstoffzufuhr unterbrochen werden.
8. Ein Verfahren nach einem der vorstehenden Ansprüche, in welchem der Katalysator eines oder mehrere der Metalle der Gruppen VB, VIB, VIIB und/oder VIII des Periodischen Systems der Elemente und/oder Verbindungen davon auf einem amorphen feuerfesten Oxid von Elementen der Gruppen II, 111 und IV des Periodischen Systems der Elemente als Träger enthält.
9. Ein Verfahren nach einem der vorstehenden Ansprüche, welches bei einer Temperatur von 300 bis 450°C, einem Gesamtdruck von 25 bis 300 bar, einem Wasserstoffpartialdruck von 25 bis 250 bar und einer Raumgeschwindigkeit von 0,1 bis 10 kg Zuspeisung pr kg Katalysator pro Stunde durchgeführt wird.
EP19830201140 1982-08-26 1983-08-01 Verfahren zur Wasserstoffbehandlung von Schweröl Expired EP0102112B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8224533 1982-08-26
GB8224533 1982-08-26

Publications (3)

Publication Number Publication Date
EP0102112A2 EP0102112A2 (de) 1984-03-07
EP0102112A3 EP0102112A3 (en) 1986-09-03
EP0102112B1 true EP0102112B1 (de) 1988-12-14

Family

ID=10532535

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19830201140 Expired EP0102112B1 (de) 1982-08-26 1983-08-01 Verfahren zur Wasserstoffbehandlung von Schweröl

Country Status (4)

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EP (1) EP0102112B1 (de)
JP (1) JPS5958090A (de)
CA (1) CA1230571A (de)
DE (1) DE3378691D1 (de)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL258576A (de) * 1959-12-04
DE1248845B (de) * 1960-05-17 1967-08-31 Shell Int Research Verfahren zur Aufheizung von Kohlenwasserstoffoelen zwecks katalytischer hydrierender Raffination
NL7406226A (nl) * 1974-05-09 1975-11-11 Shell Int Research Werkwijze en inrichting voor de hydrogenerende behandeling van een vloeibare aardoliefractie.
GB1523992A (en) * 1976-07-06 1978-09-06 Shell Int Research Process for hydrotreating of oils
JPS54103775A (en) * 1978-02-03 1979-08-15 Nippon Steel Corp Contact reactor
JPS5757790A (en) * 1980-09-25 1982-04-07 Idemitsu Kosan Co Ltd Hydrogenation treatment of heavy oil
JPS5896685A (ja) * 1981-12-03 1983-06-08 Mitsubishi Heavy Ind Ltd 水素化処理方法
JPS58149988A (ja) * 1982-03-03 1983-09-06 Mitsubishi Heavy Ind Ltd 水素化処理方法

Also Published As

Publication number Publication date
EP0102112A3 (en) 1986-09-03
JPS5958090A (ja) 1984-04-03
CA1230571A (en) 1987-12-22
EP0102112A2 (de) 1984-03-07
DE3378691D1 (en) 1989-01-19

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